Evaluation of handheld and portable Raman spectrometers with different laser excitation wavelengths for the detection and characterization of organic minerals.

Abstract

Organic minerals occur rather rarely in some types of peat bogs, sedimentary geological environments, and hydrothermal veins. Commonly, calcium oxalates are produced by several plants, terpenoids are often associated with conifers. Because of the organic precursor, these minerals, from the smallest group of the mineralogical system, are sometimes considered as biomarkers. Potential detection of these compounds has high relevance in the fields of exobiology or geobiology. Here we show the potential of four portable Raman spectrometers, using different excitation wavelengths and technologies (operating at 532, 785, and 1064nm together with an advanced spectrometer using the sequentially shifted excitation (SSE) technology), for the rapid and non-destructive identification of these phases. For the organic minerals investigated here, the most intense Raman bands are generally detected at the expected wavenumber positions ±1-4cm-1 in the region 100-2000cm-1 in the spectra obtained from all spectrometers. Additionally, two spectrometers (the 532nm instrument and the SSE) are capable of detecting Raman bands in the higher wavenumber shift region of 2000-3500cm-1, allowing the more detailed characterization and differentiation of the related phases. From this work, and on the basis of the experimental data obtained, it is clear that the longer laser excitation wavelengths are more preferable for organic minerals identification due to the better mitigation of fluorescence emission. In contrast, the Raman spectrometer equipped with the shortest excitation wavelength (532nm) gives a significantly higher spectral resolution and a more detailed discrimination of the Raman bands, provided that the conditions of general lower level of fluorescence emission are met. The results presented in the current study complement the knowledge on minerals and biomarkers of relevance for Martian environments which have been measured with mobile Raman spectrometers. The outcome creates a solid base towards the use of lightweight mobile Raman systems that can be used outdoors and on terrestrial outcrops. Moreover, these results and conclusions are of use for the further development of dedicated spectrometers destined for the instrumental suites on planetary rovers, in the frame of the forthcoming exobiology focused missions to Mars to be launched by NASA and ESA.